城市污泥添加厨余垃圾厌氧发酵产挥发性脂肪酸的研究
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摘要
城市污泥污染已经成为中国亟待解决的一个重大环境问题,采用厌氧发酵方法生产挥发性脂肪酸(VFAs)并进一步生产高附加值产品是实现污泥资源化利用的一条重要途径。在污泥中添加适量的厨余垃圾后厌氧发酵产挥发性脂肪酸可以明显提高VFAs的产量和底物的降解水平。为了考察污泥添加厨余垃圾发酵生产VFAs的特征以及预处理技术对发酵的影响,本研究在前期实验室研究的基础上,在25 L规模的厌氧发酵罐上对污泥添加厨余垃圾发酵产VFAs进行了研究,全文研究内容如下：
(1)厨余垃圾按总固体(TS)浓度为1：3的比例添加进污泥中进行厌氧发酵,考察了混合物不同TS浓度下厌氧发酵产VFAs的情况。结果显示添加厨余垃圾之后VFAs的累积量最高可达17.62g/L。综合产VFAs效果、底物降解效果和产率等情况,建议在较大规模的生产过程中选择130g/L的TS浓度为较合适的发酵产VFAs的底物浓度。对不同发酵底物浓度和产VFAs速率进行了初步的动力学研究,用Monod方程较好地拟合了产酸动力学过程,并得到动力学方程μ=(0.114·S)(281.764+S)(Ks：281.76g/L,μmax：0.114 g/h)。
(2)利用高压脉冲放电等离子体系(等离子体)和热-碱法对纯污泥和污泥添加厨余垃圾混合物进行预处理,研究了不同底物预处理过程中底物成分和性质的变化。等离子体预处理污泥时TS、VS、SCOD都有融出,但推测其中大部分是由于放电时系统温度升高从而对污泥进行热处理产生的。采用热-碱法对纯污泥和污泥厨余混合物进行预处理时TS、VS和SCOD的融出率略分别为42%、62%和72.5%。纯污泥和污泥厨余混合物的游离蛋白质的融出量分别达到64%和70.8%。游离碳水化合物的融出率均能达到50%以上。胞内物质的融出情况则是纯污泥经过热-碱预处理后胞内蛋白质融出较多,为0.019g/L；污泥厨余混合物预处理后则是胞内碳水化合物融出的较多,为0.014g/L。
(3)利用纯污泥和污泥添加厨余垃圾混合物预处理液进行发酵,研究了发酵产VFAs的情况。纯污泥和污泥添加厨余垃圾混合物经过热-碱预处理后发酵产VFAs比未经过热-碱预处理直接发酵得到的VFAs的量分别提高6.81g/L和3.30g/L,产率分别提高0.19g/gVS和0.23g/gVS。纯污泥发酵得到的是以乙酸为主要产物的VFAs,而污泥添加厨余垃圾混合物发酵后的VFA组成中乙酸和丁酸含量相当且都远大于其他单酸。在发酵过程中蛋白质比碳水化合物利用得多,游离蛋白质和游离碳水化合物是VFAs产生的主要底物来源,这其中又以游离蛋白质的贡献为主。
(4)纯污泥和污泥添加厨余垃圾混合物经过热-碱预处理后发酵的发酵液采用过滤和离心的方法进行固液分离,研究不同分离方法的分离效果。结果显示离心分离的效果优于滤布,过滤后固相含水率在80%以上,离心后固相含水率在80%以下；且污泥厨余混合物发酵液的分离效果比纯污泥发酵液的分离效果好。污泥与厨余垃圾混合经过预处理发酵后采用8000 r/min进行固液分离,从发酵液中得到的VFAs的得率最高为68.93%。
The pollution from sewage sludge has become a very serious and important environmental problem in China. Production of volatile fatty acids (VFAs) by anaerobic fermentation and further production of value added products by VFAs is one of potential strategies to realize the reuse and resource of the sewage sludge. Addition of kitchen wastes into the sewage sluge can enhance the VFAs production and substrate degradation efficiency during the anaerobic fermentation. In order to characterize the VFAs production from the mixed substrates, this study conducted the fermentation in a 25L fermentor on the basis of laboratory investigation by adding kitchen wastes into the sludge to produce VFAs The research processes and conclusions are as follows:
(1) Kitchen wastes were added into the sludge in the anaerobic fermentation with the ratio of kichen wastes and sewage sludge at 1:3. At this ratio the volatile fatty acids production under different concentrations was determined. The results showed that with the addition of the kitchen wastes, the accumulation of VFAs was up to 17.62 g/L. Based on an overall consideration of various factors, such as the VFAs production, substrate degradation and the production rates,130 g/L of TS concentration was considered the optimal fermentation substrate concentration to produce VFAs in a larger scale process. Additionally, the Monod equation was used to fit the dynamic process during anaerobic fermentation under different substrate concentrations and equation:μ=(0.114·S)/(281.764+S)(Ks:281.764 g/L,μmax:0.114 g/h) was obtained.
(2) Sewage sludge and the mixture (sludge and kitchen wastes) were pretreated by high-voltage pulsed discharge plasma systems (plasma) and thermo-alkaline respectively. The changes of substrate characteristics and composition were observed under different pretreatments. Pasma pretreatment changed the characteristics of sludge. However,it may be most attributed to the rising temperature in the system. The solubilization rate of TS, VS, SCOD are 42%,62% and 72.5%, respectively, when the mixture (sludge and kitchen wastes) substrates are pretreated by thermo-alkaline. The solubilization of dissociative protein is 64% and 70.8% respectively when the sludge and mixture (sludge and kitchen wastes) after pretreatments. Meanwhile the solubilization of dissociative carbohydrate could exceed 50%. The solubilization of intracellular material revealed that the sludge through the thermo-alkaline pretreatment released more intracellular proteins (0.019g/L), while the mixture (sludge and kitchen wastes) after hot alkaline pretreatment released more intracellular carbohydrate (0.014 g/L).
(3) The production of VFAs during fermentation after different pretreatments with pure sludge or mixed sludge was studied, respectively. After the heat-alkaline pretreatment, the VFAs from the sludge and the mixture (sludge and kitchen wastes) have increased by 6.81 g/L and 3.30 g/L, the production rates have increased by 0.19 g/gVS and 0.23 g/gVS. The main products in VFAs was acetic acid during the sludge fermenting, but we got acetic acid and butyric acid in the VFAs more than other single acids when fermented the mixture (sludge and kitchen wastes). In the process of fermentation, protein were more exploited than carbohydrates, both of them with the dissociative form were the major source of product VFAs, but the free protein was the main contribution source. (4) The method of filtration and centrifugation were used to separate the fermentation liquid after thermo-alkaline pretreatment. The effects of separation about different methods process (pretreatment, fermentation and sepration) were evaluated. The results revealed that the effect of centrifugation was better than filtration; the moisture content within solid was above 80% after filtration while the moisture conten was below 80% after centrifugation.The effect of separation about the mixture (sludge and kitchen wastes) was better than the sludge. We got the highest yield of VFAs as 68.93% when the fermentation broth of the mixture (sludge and kitchen wastes) after centrifugation.
(1)厨余垃圾按总固体(TS)浓度为1：3的比例添加进污泥中进行厌氧发酵,考察了混合物不同TS浓度下厌氧发酵产VFAs的情况。结果显示添加厨余垃圾之后VFAs的累积量最高可达17.62g/L。综合产VFAs效果、底物降解效果和产率等情况,建议在较大规模的生产过程中选择130g/L的TS浓度为较合适的发酵产VFAs的底物浓度。对不同发酵底物浓度和产VFAs速率进行了初步的动力学研究,用Monod方程较好地拟合了产酸动力学过程,并得到动力学方程μ=(0.114·S)(281.764+S)(Ks：281.76g/L,μmax：0.114 g/h)。
(2)利用高压脉冲放电等离子体系(等离子体)和热-碱法对纯污泥和污泥添加厨余垃圾混合物进行预处理,研究了不同底物预处理过程中底物成分和性质的变化。等离子体预处理污泥时TS、VS、SCOD都有融出,但推测其中大部分是由于放电时系统温度升高从而对污泥进行热处理产生的。采用热-碱法对纯污泥和污泥厨余混合物进行预处理时TS、VS和SCOD的融出率略分别为42%、62%和72.5%。纯污泥和污泥厨余混合物的游离蛋白质的融出量分别达到64%和70.8%。游离碳水化合物的融出率均能达到50%以上。胞内物质的融出情况则是纯污泥经过热-碱预处理后胞内蛋白质融出较多,为0.019g/L；污泥厨余混合物预处理后则是胞内碳水化合物融出的较多,为0.014g/L。
(3)利用纯污泥和污泥添加厨余垃圾混合物预处理液进行发酵,研究了发酵产VFAs的情况。纯污泥和污泥添加厨余垃圾混合物经过热-碱预处理后发酵产VFAs比未经过热-碱预处理直接发酵得到的VFAs的量分别提高6.81g/L和3.30g/L,产率分别提高0.19g/gVS和0.23g/gVS。纯污泥发酵得到的是以乙酸为主要产物的VFAs,而污泥添加厨余垃圾混合物发酵后的VFA组成中乙酸和丁酸含量相当且都远大于其他单酸。在发酵过程中蛋白质比碳水化合物利用得多,游离蛋白质和游离碳水化合物是VFAs产生的主要底物来源,这其中又以游离蛋白质的贡献为主。
(4)纯污泥和污泥添加厨余垃圾混合物经过热-碱预处理后发酵的发酵液采用过滤和离心的方法进行固液分离,研究不同分离方法的分离效果。结果显示离心分离的效果优于滤布,过滤后固相含水率在80%以上,离心后固相含水率在80%以下；且污泥厨余混合物发酵液的分离效果比纯污泥发酵液的分离效果好。污泥与厨余垃圾混合经过预处理发酵后采用8000 r/min进行固液分离,从发酵液中得到的VFAs的得率最高为68.93%。
The pollution from sewage sludge has become a very serious and important environmental problem in China. Production of volatile fatty acids (VFAs) by anaerobic fermentation and further production of value added products by VFAs is one of potential strategies to realize the reuse and resource of the sewage sludge. Addition of kitchen wastes into the sewage sluge can enhance the VFAs production and substrate degradation efficiency during the anaerobic fermentation. In order to characterize the VFAs production from the mixed substrates, this study conducted the fermentation in a 25L fermentor on the basis of laboratory investigation by adding kitchen wastes into the sludge to produce VFAs The research processes and conclusions are as follows:
(1) Kitchen wastes were added into the sludge in the anaerobic fermentation with the ratio of kichen wastes and sewage sludge at 1:3. At this ratio the volatile fatty acids production under different concentrations was determined. The results showed that with the addition of the kitchen wastes, the accumulation of VFAs was up to 17.62 g/L. Based on an overall consideration of various factors, such as the VFAs production, substrate degradation and the production rates,130 g/L of TS concentration was considered the optimal fermentation substrate concentration to produce VFAs in a larger scale process. Additionally, the Monod equation was used to fit the dynamic process during anaerobic fermentation under different substrate concentrations and equation:μ=(0.114·S)/(281.764+S)(Ks:281.764 g/L,μmax:0.114 g/h) was obtained.
(2) Sewage sludge and the mixture (sludge and kitchen wastes) were pretreated by high-voltage pulsed discharge plasma systems (plasma) and thermo-alkaline respectively. The changes of substrate characteristics and composition were observed under different pretreatments. Pasma pretreatment changed the characteristics of sludge. However,it may be most attributed to the rising temperature in the system. The solubilization rate of TS, VS, SCOD are 42%,62% and 72.5%, respectively, when the mixture (sludge and kitchen wastes) substrates are pretreated by thermo-alkaline. The solubilization of dissociative protein is 64% and 70.8% respectively when the sludge and mixture (sludge and kitchen wastes) after pretreatments. Meanwhile the solubilization of dissociative carbohydrate could exceed 50%. The solubilization of intracellular material revealed that the sludge through the thermo-alkaline pretreatment released more intracellular proteins (0.019g/L), while the mixture (sludge and kitchen wastes) after hot alkaline pretreatment released more intracellular carbohydrate (0.014 g/L).
(3) The production of VFAs during fermentation after different pretreatments with pure sludge or mixed sludge was studied, respectively. After the heat-alkaline pretreatment, the VFAs from the sludge and the mixture (sludge and kitchen wastes) have increased by 6.81 g/L and 3.30 g/L, the production rates have increased by 0.19 g/gVS and 0.23 g/gVS. The main products in VFAs was acetic acid during the sludge fermenting, but we got acetic acid and butyric acid in the VFAs more than other single acids when fermented the mixture (sludge and kitchen wastes). In the process of fermentation, protein were more exploited than carbohydrates, both of them with the dissociative form were the major source of product VFAs, but the free protein was the main contribution source. (4) The method of filtration and centrifugation were used to separate the fermentation liquid after thermo-alkaline pretreatment. The effects of separation about different methods process (pretreatment, fermentation and sepration) were evaluated. The results revealed that the effect of centrifugation was better than filtration; the moisture content within solid was above 80% after filtration while the moisture conten was below 80% after centrifugation.The effect of separation about the mixture (sludge and kitchen wastes) was better than the sludge. We got the highest yield of VFAs as 68.93% when the fermentation broth of the mixture (sludge and kitchen wastes) after centrifugation.
引文
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